Methine compounds

ABSTRACT

3-Cyanovinylene-10-aryl-phenoxazines and phenothiazines produce fluorescent, light-fast yellowish-orange to reddish-orange shades on polyester and cellulose acetate fibers.

United States Patent Fisher et al.

[ Dec. 17, 1974 METHINE COMPOUNDS Inventors: John G. Fisher; Curtis E.Diebert,

both of Kingsport, Tenn.

Assignee: Eastman Kodak Company,

Rochester, NY.

Filed: Feb. 7, 1973 App]. No.: 330,357

Related US. Application Data Continuation-impart of Ser. No. 215,440,Jan. 4, 1972, abandoned.

US. Cl. 260/243 A, 8/162 R, 260/240 R, 260/244 R, 260/326.44

Int. Cl C09b 23/00 Field of Search 260/240 .1, 240 R, 244 R, 260/243 AReferences Cited UNITED STATES PATENTS l/1969 Fisher et al. 260/294.9

3,453,270 7/1969 Weaver et a1 260/244 FOREIGN PATENTS OR APPLICATIONS932,343 8/1955 Germany 260/240 .1 1.003573 2/1957 Germany 260/240 JOTHER PUBLICATIONS Buu-I-Ioi et al., J. Chem. Soc., 1969, Section C, pp.2137 to 2138.

Primary ExaminerJohn D. Randolph 7 Claims, No Drawings METHINE COMPOUNDSThis invention concerns novel phenoxazine and phenothiazine methine dyeswhich are useful for dyeing polyester and cellulose acetate fibers.

Our novel methine compounds have the general formula wherein X is oxygenor sulfur;

R is cyano; alkoxycarbonyl containing from one to about nine carbonatoms; alkoxycarbonyl containing 3-5 carbon atoms substituted on thebeta, gamma or delta carbon atom with one substituent selected from thegroup consisting of lower alkoxy, hydroxy, cyano, halogen, succinimido,glutarimido; or phthalimido; lower alkylsulfonyl; arylsulfonyl; or thegroup -CONR"R in which R is hydrogen, lower alkyl, aryl or, when R ishydrogen, R also can be lower alkanoyl or lower alkoxycarbonyl and R ishydrogen or lower alkyl;

R is hydrogen, lower alkyl or lower alkoxy;

R is aryl; and

R is hydrogen, lower alkyl or lower alkoxy;

in which each aryfinoiety is phenyl, lower alkylphenyl, loweralkoxyphenyl or halophenyl.

The novel compounds of the invention produce yellowish-orange toreddish-orange shades on polyester fibers when applied thereto accordingto conventional disperse dyeing procedures. Due to their fluorescence,our compounds produce unusually bright shades, especially when dyeingsthereof are viewed under natural light. Our methine compounds alsoexhibit, in general, good fastness to light and dyeability properties.

The substituents encompassed by the generic language appearing in thedefinitions of R through R are well known in the art and can be derivedfrom known compounds according to published procedures. As used hereinto describe any alkyl moiety, lower" designates a carbon content of oneto about four carbon atoms. Chlorine and bromine are preferred halogenatoms which can be present on our novel compounds.

The methine compounds of formula (I) in which R is cyano or loweralkoxycarbonyl, R and R each is hydrogen and R is phenyl or tolyl, areespecially preferred due their excellent properties and relativeeconomy.

The novel compounds of the invention are prepared by condensing a3-formyl-lO-arylphenoxazine or a 3-formyl-l0-arylphenothiazine with anactive methylene compound having the formula NC-CH R'. The condensationgenerally is conducted under basic condi tions in an organic solvent ata temperature of 60 to 100C. For example, the reaction can beconveniently conducted in benzene at reflux using piperidine as thebasic catalyst. The methine compounds can be isolated by cooling thereaction mixture, whereupon the product crystallizes from solution.

The intermediate aldehydes are prepared by the formylation of thecorresponding IO-arylphenothiazine or lO-arylphenoxazine with aVilsmeier-type formylating agent.'Depending upon the atom represented byX and position(s) of the substituents, if any, represented by R and Rand those present on the phenyl nucleus of R. some formylation reactionsmay lead to multiple formylation products. Thus, the methine dyesprepared directly from such multiple formylation products are a mixture.The mixture of methine compounds, consisting of at least one compoundconforming to formula l can be used to produce bright dyeings asdescribed hereinabove or, in certain cases, a single methine compoundcan be obtained by isolating the 3-formyl intermediate prior tocondensation with an active methylene compound. For example, formylationof 10- phenylphenothiazine with phosphorus oxychloride andN-methylformanilide gives a mixture of 3-formyl-l0- phenylphenothiazineand 10-( 4-formyphenyl phenothiazine in a mole ratio of about 4 to l.The 3- formyl-l0-phenylphenothiazine can be obtained in a pure statefrom the aldehyde mixture by distillation and recrystallization. Thepure 3 -substituted phenothiazine dyes can then be prepared from thispurified aldehyde. The phenothiazine and phenoxazine starting materialsand the active methylene compounds are available intermediates and/orcan be prepared according to published techniques.

The following examples further illustrate the preparation of our novelcompounds.

EXAMPLE 1 3-Formyl-lO-phenylphenoxazine (1.0 g., 3.5 moles), ethylcyanoacetate (0.47 g., 4.2 moles), ethanol (25 ml.) and piperidine (1drop) are combined and heated at reflux for 3 hr. The mixture is chilledand filtered and an orange solid, ethyl a-cyano-l0-phenylphenoxazine-3-acrylate, is obtained. Yield: L22 g.; m.p. l93-l95C.; visible A 464nm. (acetone). This brilliant orange, fluorescent dye displays excellentdyeing and fastness properties on cellulose ester and polyester fibers.

EXAMPLE 2 The procedure described in Example 1 is repeated except that3-formyl-l0-phenylphenoxazine and malononitrile are employed as startingmaterials. A red solid is obtained; m.p. l89l92C.; visible A max 483 nm.(acetone). The product, l0-phenyl-3-phenoxazinylmethylenemalononitrile,produces fluorescent, orange shades and displays excellent dyeing andfastness properties on polyester fibers.

EXAMPLE 3 The procedure of Example 1 is repeated except that a mixtureof phenothiazine aldehydes and ethyl cyanoacetate are used. The orange,fluorescent material, consisting of a mixture ofl0-phenyl-3-phenothiazinylmethylenemalononitrile and'p-(l0-phenothiazinyl)- benzylidene malononitrile, obtained dyescellulose acetate and polyester fibers bright orange shades and displaysexcellent dyeing and light-fastness properties.

The methine compounds set forth in the examples of the following tableconform to formula l and are prepared by the procedures describedhereinabove. The color given for each compound refers to the shade itproduces on polyester fibers.

Ex. No. R R2, R R3 x Color H CalI Rmltlish-craugv. H -om5 m. 8-CH: CaHOrange H -CuH5 Yvllowishorange. H CeH l)(). H -on 5 Do. H 5115 D0.2.7-di-C H3 -C:ilI4-p-O C I13 range. 7-OCH3 Cnl 4-m-Cl Do. 11 -onr Do.II CnU5 D0. H -onI5 m. m 0 II cuu Do. 17. COOCHgCII(C2H )(CIIQMCH; IIcm5 m. l8 CN iLG-di-CII; C lh-p-Cll:l Rt'tldlsh-orangv. 11)..." -C()OC2U5 ll Cll li "J Orange. COOClI:C]l:OC"a ll *Cfl'll'[)'(rl 3 W [)n.so' (um n Gill ON -s [)o. 21 C()()(C"2)JCH1 4.1-dl-Cll3 (,|il| pCll:i AS[)t.

23 if -Cnllt-Il-CH1 S D0.

-00ocincnmoooincrnoo l NC O The po yester and cellulose acetate fiberswhich can be dyed with our novel compounds and the techniques C=CH-$ w 0O by which our compounds are applied are well known in NC a g the art,See, for example, French Pat. No. 2,088,404 20 and US Pat. No. 3,491,082and 3,553,245. 1

This invention has been described in detail with particular reference tocertain preferred embodiments f w thereof, but it will be understoodthat variations and Q 0 modificationsmay be made without departing fromthe 25 s irit and sco e of the invention as described hereinqgove p 4. Acompound according to claim 1 having the fora We claim: mula NC O Q l. Acompound of the general formula fl fi CsHsOOC 0 f U m I ll ll T i R1 C OO O Q 7 R2 f O 5. A compound according to claim 1 having the formula NCS 4O wherein (3:01P? w f X is ox en or sulfur- O 0 O O 1 yg y R IScyano, alkoxycarbonyl containing from one to N about nine carbon atoms;alkoxycarbonyl containl ing 3-5 carbon atoms substituted on the beta,gamma or delta carbon atom with one substituent selected from the groupconsisting of lower alkoxy, hydroxy. cyano, halogen; loweralkylsulfonyl; arylsulfonyl; or the group --CONR*R" in which R ishydrogen, lower alkyl, aryl or, when R is hydro- 5O gen, R also can belower alkanoyl or lower alkoxycarbonyl and R is hydrogen or lower alkyl;

R is hydrogen. lower alkyl or lower alkoxy;

R is aryl: and

R is'hydrogen, lower alkyl or lower alkoxy; 5

in which each a ryl 111615; is phenylf'lo wer alkylphenyl. loweralkoxyphenyl or halophenyl.

2. A compound according to claim 1 wherein X is oxygen or sulfur;

R is cyano; alkoxycarbonyl containing from one to about nine carbonatoms; lower alkylsulfonyl; arylm sulfonyl; or the group COl lR*R inwhich R is hydrogen, lower alkyl, aryl or, when R is hydrogen. R alsocan be lower alkanoyl or lower alkoxy- 6S carbonyl, and R is hydrogen orlower alkyl; R is hydrogen, lower alkyl or lower alkoxy; R is aryl; andR is hydrogen, lower alkyl or lower alkoxy. 3. A compound according toclaim 1 having the formula 6. A compound according to claim 1 having theformula 7. A compound according to claim 1 having the forula

1. A COMPOUND OF THE GENERAL FORMULA
 2. A compound according to claim 1 wherein X is oxygen or sulfur; R1 is cyano; alkoxycarbonyl containing from one to about nine carbon atoms; lower alkylsulfonyl; arylsulfonyl; or the group -CONR4R5 in which R4 is hydrogen, lower alkyl, aryl or, when R5 is hydrogen, R4 also can be lower alkanoyl or lower alkoxycarbonyl, and R5 is hydrogen or lower alkyl; R2 is hydrogen, lower alkyl or lower alkoxy; R3 is aryl; and R6 is hydrogen, lower alkyl or lower alkoxy.
 3. A compound according to claim 1 having the formula
 4. A compound according to claim 1 having the formula
 5. A compound according to claim 1 having the formula
 6. A compound according to claim 1 having the formula
 7. A compound according to claim 1 having the formula 